WO2020157228A1 - Liant pour une composition de revêtement aqueuse - Google Patents

Liant pour une composition de revêtement aqueuse Download PDF

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Publication number
WO2020157228A1
WO2020157228A1 PCT/EP2020/052343 EP2020052343W WO2020157228A1 WO 2020157228 A1 WO2020157228 A1 WO 2020157228A1 EP 2020052343 W EP2020052343 W EP 2020052343W WO 2020157228 A1 WO2020157228 A1 WO 2020157228A1
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WIPO (PCT)
Prior art keywords
groups
polymer
hydroxy
mol
water
Prior art date
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PCT/EP2020/052343
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English (en)
Inventor
Armin Temel
Florian Lunzer
Robert Potzmann
Richard Hendrikus Gerrit Brinkhuis
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Allnex Austria Gmbh
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Publication date
Priority claimed from EP19155169.6A external-priority patent/EP3689986A1/fr
Priority claimed from EP19163580.4A external-priority patent/EP3712190A1/fr
Application filed by Allnex Austria Gmbh filed Critical Allnex Austria Gmbh
Priority to AU2020215259A priority Critical patent/AU2020215259A1/en
Priority to EP20701655.1A priority patent/EP3918017A1/fr
Priority to KR1020217026809A priority patent/KR20210122265A/ko
Priority to CN202080011529.7A priority patent/CN113366069B/zh
Priority to JP2021544531A priority patent/JP7486501B2/ja
Priority to US17/423,002 priority patent/US20220098406A1/en
Priority to CA3125005A priority patent/CA3125005A1/fr
Publication of WO2020157228A1 publication Critical patent/WO2020157228A1/fr

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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
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    • C08L75/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/0842—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents
    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0866—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being an aqueous medium
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    • C08G18/0861—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers
    • C08G18/0871—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic
    • C08G18/0876—Manufacture of polymers in the presence of non-reactive compounds in the presence of liquid diluents in the presence of a dispersing phase for the polymers or a phase dispersed in the polymers the dispersing or dispersed phase being organic the dispersing or dispersed phase being a polyol
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    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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    • C08G18/3271—Hydroxyamines
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    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4202—Two or more polyesters of different physical or chemical nature
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
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    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
    • C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
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    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
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    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
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    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Definitions

  • the invention relates an aqueous oligomer or polymer dispersion wherein the dispersed oligomer or polymer comprises an average of at least two Michael donor groups in an oligomer or polymer molecule, and is a self-emulsifying oligomer or polymer which comprises incorporated moieties that have pending hydrophilic groups, or hydrophilic groups which form part of the oligomer or polymer chain, wherein the Michael donor groups are addic C-H groups from activated methylene >CH2 and/or methine oCH groups, also referred to by the IUPAC systematic name as "methylidene" for the former, and "methylylidene” or “methanylylidene” for the latter.
  • the invention also relates to the self- emulsifying oligomer or polymer and to a process for the preparation of the said self- emulsifying oligomer or polymer and the said aqueous oligomer or polymer dispersion which has an average of at least two Michael donor groups in an oligomer or polymer molecule, and to a binder for an aqueous coating composition comprising as a first component, the said aqueous oligomer or polymer dispersion which has an average of at least two Michael donor groups in an oligomer or polymer molecule, and a second component hereinafter referred to as "Michael acceptor" which is at least one organic compound having at least two activated olefinically unsaturated groups, wherein activation of the unsaturated group is effected by at least one electronegative group
  • the Michael donor is a water-dispersible oligomer or polymer, or both the Michael donor and the Michael acceptor are water-dispersible oligomers or polymers, or both Michael donor groups and Michael acceptor groups are present in a water-dispersible oligomer or polymer.
  • the invention also relates to a coating composition
  • a coating composition comprising a non-polymeric and non-oligomeric Michael donor component which has an average of at least two Michael donor groups in its molecule, and as a second component, an aqueous dispersion of an oligomeric or polymeric Michael acceptor component, wherein the dispersed oligomer or polymer comprises an average of at least two Michael acceptor groups in an oligomer or polymer molecule, and is an externally emulsified oligomer or polymer or a self-emulsifying oligomer or polymer which comprises incorporated moieties that have pending hydrophilic groups, or hydrophilic groups which form part of the oligomer or polymer chain.
  • Binders for coating compositions comprising Michael donor and Michael acceptor compo nents which are cured by a Michael addition reaction between donor and acceptor have already been described in the past, such as by Noomen in Progress in Organic Coatings, vol. 32 (1997), pages 137 to 142.
  • Coating compositions are disclosed therein which are based on a first system which comprises a malonate functional polyester resin, synthesised from pentane-diol and diethylmalonate, with an "equivalent weight: 195", the reaction product of 1 mol of the triisocyanurate of isophorone diisocyanate and 3 mol of hydroxybutyl acrylate, which system is catalysed with l,8-diaza-bicydo[5,4,0]undec-7-ene (DBU), see section 2.1; a second system which comprises the said malonate polyester in combination with an unsaturated urethane acrylate, catalysed with DBU, see section 2.2; and a third system which comprises the said malonate polyester in combination with the reaction product of 1 mol of isophoronediisocyanate and 2 mol of hydroxy-butyl acrylate, catalysed with DBU, see section 2.3.
  • a first system which comprises
  • Ambient-temperature-curable aqueous polymer systems comprising: (A) an acetoacetylated polymer; and (B) a polyacrylate containing at least two (meth)acrylate end groups, in the form of an aqueous solution, suspension, or emulsion, wherein said acetoacetylated polymer is a water- dispersible acetoacetylated acrylic resin obtained by solution copolymerisation of a mass fraction of from 10 % to 60 % of a (meth)acrylic monomer (Ml) having the formula
  • CH 2 C(R 1 )-C(0)-0-R 2 -0-C(0)-CH 2 -C(0)-CH 3 (Ml), wherein R 1 is -H or -Chh and R 2 is a linear or branched saturated Ci- to C 4 - alkylene group, a mass fraction of from 1 % to 15 % of a carboxyl vinyl monomer (M2), and a mass fraction of from 25 % to 89 % of a copolymerisable vinyl monomer (M3) selected from the group con sisting of Ci- to C 4 -alkyl (meth)acrylate, and styrene.
  • a further embodiment claimed in claim 10 is an ambient-temperature curable composition, comprising: (A) a compound containing at least two acetoacetate methylene groups; (B) a compound containing at least two acrylate alkene groups; (C) a compound containing at least two epoxy groups; and (D) a Michael reaction catalyst base.
  • Systems are disclosed which comprise an acetoacetylated polymer (A) in the form of an acrylic water-dispersible resin or an acrylic latex, and a polyacrylate having at least two (meth)acrylate end groups.
  • the acetoacetylated acrylic water-dispersible resins are made by copolymerisation of a monomer mixture comprising mass fractions of from 10 % to 60 % of an acetoacetylated (meth)acrylate monomer, from 1 % to 15 % of a hydrophilic vinyl monomer, and from 25 % to 89 % of other copolymerisable vinyl monomers, and the aceto-acetylated acrylic latices are made by emulsion polymerisation of these monomers as stated supra.
  • the polyacrylate having at least two (meth)acrylate end groups used as crosslinker is preferably a NCO-free water dispersible urethane polyacrylate resin.
  • NCO-terminated prepolymer are prepared by a two-stage process wherein a water-dispersible NCO-terminated prepolymer is formed in the first stage by reacting an excess of a polyisocyanate with an hydrophilic NCO- reactive compound which can impart the desired water dispersibility and/or a further NCO- reactive compound other than the hydrophilic compound mentioned supra.
  • the NCO- terminated prepolymer is then capped with (meth)acrylate functionality by reacting with a NCO-reactive (meth)acrylate in a second stage.
  • Suitable catalysts used are bases having a pKa of from 12 to 14, such as l,8-diazabicydo[5,4,0]undecene-7 (DBU), 1,5- diazabicy do [4,3,0] nonene-5 (DBN), 1,1,3,3-tetramethylguanidine (TMGD), 1,4- dihydropyridines, 2-allyl-N-alkyl imidazolines, tetra-t-butylammonium hydroxide, potassium methoxide, sodium hydroxide, and potassium hydroxide.
  • DBU l,8-diazabicydo[5,4,0]undecene-7
  • DBN 1,5- diazabicy do [4,3,0] nonene-5
  • TMGD 1,1,3,3-tetramethylguanidine
  • 1,4- dihydropyridines 2-allyl-N-alkyl imidazolines, tetra-t-butylammonium hydroxide, potassium methoxide,
  • indude low molar mass poly-malonates useful as curing agents indude trimethylolpropane tri(ethyl malonate) which can be prepared by transesterification of trimethylolpropane with diethyl malonate.
  • High molar mass polymalonates indude malonated polyesters obtained by condensation polymerisation of malonic adds with glycols and other dibasic adds.
  • a water-borne coating composition comprising a vinyl polymer having acetoacetate functional groups and a polyalkyleneimine as stabiliser against gelling, optionally, crosslinkers such as trimethylol propane tri(meth)acrylate, 1,6-hexanediol di(meth)acrylate, and allyl acrylate, together with an anionic surfactant which is added after polymerisation, has been described in WO 1999/014278 Al, corresponding to US 6,201,048 Bl.
  • a main concern in low temperature curing systems is the mobility of the components which carry the groups responsible for the curing reaction. This mobility is restricted during the film formation and vitrification of the coating film during the first stage of crosslinking. Further crosslinking can be enhanced by keeping the reactive groups in near neighbourhood. This can be done, e. g., by induding both kinds of reactive groups in the same emulsified droplet, or even in the same polymer chain. An extended potlife together with rapid curing after application is therefore desired.
  • the Michael reaction is a nucleophilic addition of a carbanion (or another nucleophile) to an alpha, beta-unsaturated compound bearing electron-withdrawing groups, which unsaturated compound is referred to as Michael acceptor.
  • a Michael donor component that forms the nucleophile by deprotonation in the context of the present invention is an organic molecule which has at least one addic C-H group which is a C-H group in activated methylene >CH2 group with a carbon atom attached to two further atoms which are not hydrogen, and methine oCH groups with a carbon atom attached to three further atoms which are not hydrogen, where at least one of the substituents is an electronegative substituent stabilising the carbanion, such as carboxyl groups, carbonyl groups, nitro groups, and cyano groups.
  • the present invention therefore relates to a water dispersible self-emulsifying polymer US comprising Michael donor groups, which polymer US comprises incorporated moieties that have pending hydrophilic groups and/or hydrophilic groups which form part of the polymer chain, and which comprises in its polymer chain ester groups or urethane groups, or both, as parts of the repeating units, and further preferably has a number average molar mass of at least 500 g/mol, and wherein the Michael donor groups are acidic C-H groups from activated methylene and/or methine groups, the carbon atom of the addic C-H group being attached to at least one electronegative substituent, or electron-withdrawing group, wherein the polymer US, comprises, on average, at least two addic C-H groups per molecule, and wherein the specific amount of substance of addic C-H groups in the polymer US is at least 0.5 mol/kg and wherein the amount of addic C-H groups in the polymer US is derived in majority from malonate moie
  • an aqueous polymer dispersion wherein the dispersed polymer U comprises Michael donor groups, and is a self-emulsifying polymer US which comprises in its polymer chain ester groups or methane groups, or both, as parts of the repeating units, and further preferably has a number average molar mass of at least 500 g/mol, and comprises incorporated moieties that have pending hydrophilic groups and/ or hydrophilic groups which form part of the polymer chain, wherein the Michael donor groups are addic C-H groups from activated methylene and/or methine groups, the carbon atom of the addic C-H group being attached to at least one electronegative substituent, or electron-withdrawing group, such as carboxyl groups, carbonyl groups, and cyano groups, wherein the polymer US comprises, on average, at least two addic C-H groups per molecule, and wherein the specific amount of substance of addic C-H groups in the polymer US is at least 0.5 mol/kg and
  • polymer By polymer is understood in the present invention an oligomer or polymer comprising at least 2 repeating units, preferably at least 5 repeating units.
  • a repeating unit in the context of the present invention, is a part of a polymer whose repetition would produce at least a part of the complete polymer chain, except for the end groups, by linking the repeating units together successively along the polymer chain.
  • aqueous polymer dispersion a dispersion of a polymer, usually in the form of dispersed partides, in an aqueous phase.
  • the aqueous polymer dispersion comprises preferably at least 10 % by weight of water.
  • the relative weight ratio of water to the solid polymer US in this dispersion being at least 10 weight % (wt%), preferably at least 15 wt% and more preferably at least 25 wt%.
  • the relative ratio of water to the solid polymer US usually does not exceed 95 wt%, preferably does not exceed 75 wt%.
  • the polymer US comprises, in its polymer chain, moieties derived from a monomeric, oligomeric, or polymeric hydroxy-functional component B having at least one acidic C-H group, and moieties derived from a monomeric, oligomeric, or polymeric component D which is either an acid-functional component Da, or an isocyanate-functional component Di.
  • the polymer US comprises ester groups or urethane groups as repeating units, when using Da or Di as component D.
  • the polymer US comprises, in its polymer chain, moieties derived from an at least difunctional add Ba having at least one addic C-H group, and moieties derived from a monomeric, oligomeric, or polymeric hydroxyfunctional component Dh which is preferably a hydroxy-functional component Bh as explained infra.
  • the polymer US comprises ester groups as repeating units, when using Bh as component D.
  • the polymer US can be made by reacting a hydroxy-functional component B having, on average, at least one addic C-H group per molecule as Michael donor, and at least two hydroxyl groups per molecule, and an at least difunctional component D which is either an acid-functional component Da, or an isocyanate-functional component Di, that react with hydroxyl groups of component B by collective or consecutive or mixed reaction, under polyaddition to form a polyurethane, or under poly-condensation to form a polyester.
  • the polymer US is preferably a polyester, where the additional reaction step with the acid-functional component Da is avoided.
  • This polyester is preferably formed, especially by a transesterification process, from a component B0 which is an ester, preferably of an alkanol having from one to six, more preferably from one to four, carbon atoms, and an at least difunctional organic acid Ba as defined infra having at least one acidic C-H group, the carbon atom of which is attached to carbon atoms having electronegative substituents, such as carboxyl groups, carbonyl groups, and cyano groups, with a hydroxyfunctional component Dh which is preferably a hydroxy-functional component Bh as explained infra.
  • alkanol is liberated in the transesterification process.
  • alkenol esters of Ba such as isopropenylester could be used in stead of alkanol esters, in which case an alkenol is released after transesterification as a ketone.
  • the oligomeric or polymeric hydroxy-functional Michael donor component B having addic C-H groups are preferably polyesters made from dibasic organic adds Ba having at least one addic C-H group which is attached to a carbon atom having electronegative substituents, such as carboxyl groups, carbonyl groups, and cyano groups, more preferably selected from the group consisting of oligomeric esters or polyesters BM comprising malonate groups, according to formula - O - C(O) - CH 2 - C(O) - O -, which can be synthesised, e.
  • dialkyl malonates Bm with organic dihydroxy compounds Bh, which are preferably linear or branched aliphatic or cydoaliphatic diols, in the presence of transition metal catalysts, such as compounds of titanium, zirconium, tin, hafnium, antimony, and bismuth.
  • Preferred adds Ba are malonic add, alkylmalonic adds, acetylacetone dicarboxylic acid, an other beta-ketocarboxylic adds and beta-ketodicarboxylic acids.
  • Single diols Bh, or mixtures of two or more than two diols can be used.
  • cydoaliphatic or branched aliphatic diols Bh having from five to fifteen carbon atoms, wherein at least one is preferably selected from the group consisting of neopentylglycol, 1,2-, 1,3- and 1,4-bishydroxymethyl-cydohexane, 2-sec-butyl-2-methyl- propanediol-1,3, 2-butyl-2-ethyl-propanediol-l,3, 2-ethyl-propane-diol-l,3, 2-butyl-2-methyl- propanediol-1,3, 2,6-bishydroxymethyl-decahydro-naphthalene, and the isomer mixture of TCD alcohol (tricydodecanedimethanol or octahydro-4,7-methano-lH-indene-dimethanol, systematic name: 3(4),8(9)-dihydroxymethyl-tricydo(5.2.1.02.6)decane, mixture of is
  • dialkyl malonates Bm those having alkyl groups of from one to four carbon atoms are preferred, such as dimethylmalonate, diethylmalonate, di-n-propylmalonate, diisopropyl-malonate, di-n-butylmalonate, and diisobutylmalonate.
  • Preferred other electron-withdrawing groups are cyano groups, carbonyl groups, and nitro groups.
  • triols B'h3 the triols B21h as mentioned infra can preferably be used. It is also possible to use a polyesterpolyol or a polyetherpolyol having both hydroxyl end groups, and end groups which are esters of a monofunctional beta-keto add B'ak, or of a monofunctional aliphatic acid B'aw, as mentioned supra. There must be, of course, at least one hydrogen atom bound to the alpha-carbon atom of the add B'a.
  • the diadd component Bs in the polyester polyol is an aliphatic or aromatic diadd having at least four, and not more than twelve carbon atoms, preferably selected from the group consisting of sucdnic add, adipic add, 1,2-, 1,3-, and 1,4-cydohexanedicarboxylic acid, terephthalic add, and isophthalic add.
  • polyesters BM comprising malonate groups, according to formula - O - C(O) - Chh - C(O) - O -, which are prepared by a polycondensation directly from malonic add or preferably, from alkyl esters of malonic add Bm, with cydoaliphatic or branched aliphatic diols Bh having from five to fifteen carbon atoms, wherein at least one is preferably selected from the group consisting of neopentylglycol, 1,2-, 1,3- and 1,4-bishydroxymethylcydohexane, 2-sec-butyl-2-methyl- propanediol-1,3, 2-butyl-2-ethyl-propanediol-l,3, 2-ethyl-propane-diol-l,3, 2-butyl-2-methyl- propanediol-1,3, 2,6-bishydroxymethyldecahydronaphthalene, and the iso
  • oligomeric or polymeric diols such as polyalkyleneglycol diols having from two to six carbon atoms in the alkylene group, and also by polyester polyols or polycarbonate polyols which have preferably two hydroxyl groups per molecule.
  • the oligomeric esters or polyesters BM comprising malonate groups can be reacted with an isocyanate-functional component Di, optionally together with further hydroxy-functional components as detailed infra under "Optional Components in the Polymeric Michael Donor", to obtain a mixed polyester- polyurethane.
  • the Michael donor can also be selected from reaction products of a monomeric dihydroxy- functional component B2 having addic C-H groups, selected from the group consisting of hydroxy-functional diesters B22 of one mole of a dibasic carboxylic add B22a having C-H addic hydrogen groups with two moles of at least dihydric aliphatic alcohols B22h, such as bis-2-hydroxyethylmalonate, and monoesters B21 of triols B21h which are esterified with C- H addic monocarboxylic adds B21a, preferably triols B21h that have at least two hydroxymethyl groups bound to the same carbon atom, such as glycerol and trimethylolalkanes acetoacetic add or cyanoacetic add or their reactive derivatives, such as glycerol monoacetoacetate, trimethylolalkane monoacetoacetate or glycerol monocyanoacetate and trimethylolalkane monocyanoacetate where the trimethylo
  • Polyesters U'EE comprising malonic add groups can be made via transesterification from dialkylmalonates or other reactive derivatives of malonic add, optionally together with other difunctional adds or readive derivatives therefrom, and organic compounds B22h2 having two hydroxyl groups in a molecule, or mixtures of more than one of such compounds.
  • Polyesters U'EE comprising other moieties with addic C-H groups can be made by polycondensation reaction of aliphatic dicarboxylic adds B22a having from four to forty, preferably six to thirty-six carbon atoms, preferably selected from the group consisting of adipic add, an dimer fatty acids, or aromatic dicarboxylic adds having from eight to twelve carbon atoms, such as terephthalic add, isophthalic add, and 1,4-, 2,3-, and 2,6-naphthalene dicarboxylic adds, with monoesters B21 of triols B21h which are esterified with C-H addic monocarboxylic adds B21a, preferably triols B21h that have at least two hydroxymethyl groups bound to the same carbon atom, such as glycerol and the trimethylolalkanes trimethylolethane, trimethylolpropane, trimethylolbutane and trimethylolpentane, with
  • the polyester For use in the polymer U'S, which is in this case a self-emulsified polyester U'SE, the polyester must also comprise hydrophilic moieties derived from additional monomers used in the polycondensation process, which are built into the polymer chain, or moieties that are attached to the polymer chain by reaction with the end groups of the polyester, i. e. either a hydroxyl group, or an add group.
  • Other useful monomeric mono-hydroxy-functional components B1 having addic C-H groups are monohydroxy esters of dihydric alcohols with adds having addic C-H groups such as acetoacetic acid and cyanoacetic add or monoalkylmalonates, e. g., 2- hydroxyethylaceto-acetate, 2-hydroxypropylacetoacetate, 2-hydroxyethylcyanoacetate and 2- hydroxyethyl-monoethyl-malonate, which hydroxyesters B1 can become end groups of a polymer chain.
  • a reaction product of one molecule of D and two molecules of B1 can be used as oligomeric Michael donor component.
  • the self-emulsifying polymer US differs from an externally emulsified polymer UE in that it has, additionally, as further constituents in the polymer chain, structural elements of compounds A that have hydroxyl groups as functional groups, and moieties which are hydrophilic, and can be nonionic if derived from compounds An, or anionic if derived from compounds Aa, or can have both anionic and nonionic substructures if derived from compounds Aan. These structural elements have pending hydrophilic groups as end groups or side chains, or hydrophilic groups which form part of the polymer chain.
  • Compounds Anl have either only one hydroxyl group, designated as Anil, whereby they can be located at the polymer chain end, to be a terminal hydrophilic entity, or they have two or more hydroxyl groups, designated as Anl2, which allows them to be built into the polymer chain, and form pendant hydrophilic moieties.
  • the hydroxy-functional hydrophilic component A is preferably selected from the group consisting of
  • a component Aa which has at least one, preferably two, hydroxyl groups and an add group, which is preferably sterically hindered
  • Anl which is a monoalkylether of a polyoxyalkylene glycol having from one to four carbon atoms in the alkyl group, and from two to four carbon atoms in the alkylene group which is linear or branched, preferably two carbon atoms in the alkylene group which is linear or branched, and where the polyoxyalkylene group is bound with the remaining hydroxyl group by an ether bond to
  • a dihydric alcohol to yield a monohydroxy -functional component Anil, or an at least trihydric alcohol, preferably a trihydric alcohol, to yield a dihydroxy -functional, or higher functional component Anl2,
  • the self-emulsifying polymer US being a poly urethane
  • hydrophilic groups which comprise lateral polyoxyalkylene chains by addition of polyoxyalkylene glycol monoethers AnOl, preferably monoalkyl polyethylene glycol, and using also trifunctional isocyanates Di3 in the synthesis of the self-emulsifying polyurethane where the amount of the Di3 has to be chosen to compensate for the presence of AnOl, viz., the amount of substance of Di3 should be approximately equal to the amount of substance of AnOl: «( Di3) ⁇ «(AnOl), where approximately equal means that the ratio «(Di3) / «(AnOl) is : 0.7 ⁇ «(Di3) / «(AnOl) ⁇ 1.3.
  • Preferred nonionic hydrophilic moieties are derived from oligomeric or polymeric oxyalkylene ethers, wherein the alkylene groups have from two to four carbon atoms and are linear or branched, preferably they have two or three carbon atoms, or they are derived from copolymers having both oxyethylene and oxypropylene moieties, and most preferred, from homopolymers consisting of oxyethylene groups only.
  • such oligomers have up to ten repeating units, and such polymers have at least eleven repeating units.
  • the nonionic hydrophilic group can form a part of the polymer chain, as in the case of, e.
  • a polyoxyethylene diol having one hydroxyl group at each end of its chain, or it can be a pending group where there are at least two hydroxyl groups close together at one end of polyoxyethylene chain, and no other reactive hydroxyl group at the other end of the chain.
  • nonionic hydrophilic moieties can be introduced into the polymer by reaction of nonionic hydrophilic compounds Anl including both Anil and Anl2, or An2, collectively referred to as Anh, having hydroxyl groups as functional groups, or by reaction of nonionic hydrophilic compounds Ant having functional groups that react with hydroxyl groups to form ester bonds or urethane bonds in the polymer chain of US.
  • Preferred nonionic hydrophilic compounds Anl2 are dihydroxy-functional monoethers of trimethylolalkanes having from torn to ten carbon atoms with monohydroxy-functional oligomeric or polymeric oxyalkylene alkyl ethers, where the alkyl group has preferably from one to four carbon atoms, and the alkylene groups have from two to four carbon atoms, preferably two to three, particularly preferred, two, or can be copolymers having oxyethylene and oxypropylene units, in random or block copolymer form. Particularly preferred are compounds Anl2 which are ethers of formula
  • R is an alkyl group preferably having from one to four carbon atoms, preferably selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso butyl, sec-butyl and tert-butyl, particularly preferred, methyl,
  • R' is H, or an alkyl group having from one to seven carbon atoms, preferably methyl, ethyl, n-propyl, and n-butyl, and
  • n is an integer number of at least 5, preferably from 10 to 50.
  • the amount of Anl2 in the polymer US is preferably such that the amount of oxyalkylene, especially oxyethylene, in the overall polymer US is from 5 to 50 weight %, more preferably from 10 to 30 wt% and most preferred from 12 to 20 wt%.
  • the amount of Anl2 in the polymer US is preferably such that the amount of oxyalkylene, especially oxyethylene, in the overall polymer US is from 5 to 150 g per mol of addic C-H group, more preferably from 10 to 100, and most preferred from 10 to 75 g per mol of addic C-H group.
  • nonionic emulsifying moieties in the polyurethane allows to avoid introdudng the hydroxycarboxylic or aminosulphonic adds usually used to make polyurethanes water-dispersible. It was also found that combinations of these non-ionic hydrophilic agents with the said hydroxycarboxylic or aminosulphonic adds Aa, particularly with bis-hydroxymethylpropionic add, work well, and the amount of substance of such hydrophilic agents can be reduced if a mixture of non-ionic and anionic hydrophilisation is used. It is also possible to introduce polyether polyols based on dihydroxypolyoxyalkyleneglycols which are linear or branched into the polymer chain. Particularly preferred are poly oxyethylene glycols having a molar mass horn 500 g/mol to 4000 g/mol.
  • Preferred anionic hydrophilic moieties are those that have at least one anionic group, or at least one group that can be converted to an anionic group by salt formation (neutralisation), derived horn compounds having anionic groups, or are able to form anionic groups when reacted with an alkaline substance.
  • One further reactive group is needed in the compounds Aa to incorporate this moiety into the polymer, to form an end group, and two further reactive groups are needed for incorporation into the polymer chain in addition to those groups that are needed to incorporate these moieties into the polymer chain in a non terminal position.
  • the further reactive group is preferably a hydroxyl group, that can react with an add-functional component Da to form an ester bond, or that can react with an isocyanate-functional group Di to form a urethane bond; or an amino group which may be primary or secondary, and that can react with an acid-functional component Da to form an amide bond, or that can react with an isocyanate-functional group Di to form a urea bond.
  • Preferred compounds Aa are therefore hydroxy adds Aha having one or preferably two hydroxyl groups, the add group preferably being a carboxyl group - C(O) - OH, such as 2,2- bis-hydroxymethylacetic add and its homologues, or a sulfonic acid group— S (O2) - OH, and amino adds Aaa having one or two primary and/or secondary amino groups, such as 2- aminoethyl-2-aminoethane sulfonic add.
  • These polymers US are preferably made horn a hydroxy-functional component B having, on average, at least one addic C-H group per molecule as Michael donor, and least two hydroxyl groups per molecule, and an at least difunctional component D that reacts with hydroxyl groups of component B, and additionally, horn compounds A that can be incorporated into the polymer chain by reaction of their hydroxyl groups, in the case that hydroxy-functional compounds Ah are used, with functional groups of components D, or by reaction of functional groups that can react with hydroxyl groups of component B, in the case that compounds At are used that can react with hydroxyl groups, by collective or consecutive or mixed reaction, under polyaddition or polycondensation.
  • a hydroxy-functional component A having at least one hydroxyl group and at least one hydrophilic group is incorporated into the polymer made horn a polymeric hydroxy- functional component B having Michael donor groups as defined supra and a monomeric, oligomeric, or polymeric at least difunctional component D as defined supra that reacts with hydroxyl groups of component B by collective or consecutive or mixed reaction, under polyaddition or poly condensation.
  • the hydroxy -functional component A can be a dihydroxy compound derived from a polyoxyalkylene which is hydrophilic, preferably polyoxyethylene and copolymers comprising oxyethylene and oxypropylene moieties, as block copolymers, or as random copolymers.
  • a polyoxyethylene diol which can be incorporated into the polymer US by reaction of the terminal hydroxyl groups with component D during he polymer synthesis.
  • a very efficient method for providing the needed hydrophilidty is the use of a reaction product Ay of a trimethylolalkane whereof only one hydroxyl group is part of an ether bond with a polyoxyethylene chain, the other terminal hydroxyl group of the polyoxyethylene chain being etherified preferably with a Ci- to C 4 - alkyl group, and the remaining two hydroxyl groups of the trimethylolalkane which had been temporarily protected during the ethoxylation step serve to incorporate this compound Ay into the polymer chain.
  • trimethylolalkane tris-hydroxymethylmethane, 2, 2-bishy droxymethylpropane-l-ol, 2, 2-bishy droxymethylbutane-l-ol, and 2,2- bishy droxymethyl-pentane-l-ol are preferably used.
  • These hydrophilic modifiers Ay can be combined with the dihydroxy carboxylic adds Aa mentioned supra, wherein a synergy has been noted between these two types of hydrophilic agents.
  • moieties derived from further hydroxy-functional components B" can also present in the polymer chain of polymer US.
  • These further hydroxy-functional components B" can be polymeric, such as polyesterdiols BE made from aliphatic or aromatic dicarboxylic adds BEa with organic dihydroxy compounds BEh, preferably linear or branched aliphatic, or cydoaliphatic diols, and polycarbonatediols BC made from reactive derivatives of carbonic add induding dialkyl carbonates, alkylene carbonates, and carbonyl halogenides with organic dihydroxy compounds BEh, preferably linear or branched aliphatic, or cycloaliphatic diols having from four to ten carbon atoms.
  • hydroxy-functional components B" which are preferably selected from low molar mass aliphatic linear, branched or cyclic dihydroxy compounds B"h having a molar mass not exceeding 600 g/mol, polycarbonatediols BC made from reactive derivatives of carbonic add inducting dialkyl carbonates, alkylene carbonates, and carbonyl halogenides with organic dihydroxy compounds BEh, which are preferably linear or branched aliphatic, or cycloaliphatic diols having from four to ten carbon atoms, and/or polyesterdiols BE having a molar mass higher than 600 g/mol, made by poly condensation of aromatic or aliphatic linear, branched or cydic dicarboxylic adds B"a or anhydrides thereof, and aliphatic linear, branched or cydic dihydroxy compounds BEh, wherein the stoichiometry in the polycon
  • the hydroxy -functional component B"h having at least two hydroxyl groups per molecule is preferably selected from the group consisting of aliphatic linear, branched or cydic diols having at least two carbon atoms, and preferably not more than forty carbon atoms, preferably, ethylene glycol, 1,2- and 1,3-dihydroxypropane, 1,2-, 1,3- and 1,4- dihydroxybutane, 1,5-dihydroxy-pentane, neopentylglycol, 1,6-dihydroxyhexane, 3- methylpentane-l,5-diol, 1,2- and 1,8-dihydroxyoctane, 2,2,4-trimethylpentane-l,3-diol, 1,2- and 1,12-dodecanediol, 1,2- and 1,-16-hexadecanediol, 1,2- and 1,18-octadecanediol, and dimer diols made from dimer
  • the specific amount of substance of addic C-H groups in the polymer US is usually at least 1 or even at least 1.8 mol/kg.
  • the specific amount of substance of addic C-H groups in the polymer US is preferably at least 1.2, more preferably at least 1.4, most preferably at least 2.0 and even more preferably at least 2.5 mol/kg.
  • the amount of addic C-H groups in the polymer US is preferably derived in majority from malonate moieties.
  • the specific amount of substance of addic C-H groups in the polymer US provided from malonate moieties is preferably at least 0.5, more preferably at least 1.0, most preferably at least 1.5 and even more preferably at least 1.9 mol/kg.
  • the specific amount of substance of addic C-H groups in the polymer US does preferably not exceed 12.5, more preferably not 10.0 mol/kg.
  • the polymer US more preferably has a number average molar mass of at least 700, most preferably of at least 1400 g/mol.
  • the molar mass of polymer US usually does not exceed 5000 g/mol.
  • the polymer US more preferably has a mass average molar mass of at least 2000 g/mol.
  • the mass average molar mass of polymer US usually does not exceed 20000 g/mol.
  • the polymer US is preferably a polyester UE which is self-emulsified (UES), having ester groups -C-0-C(0)-C- in the polymer chain, which ester groups can be formed in a polycondensation reaction from polymeric hydroxy-functional compounds B having at least two hydroxyl groups per molecule, and from add-functional compounds Da having at least two acid groups per molecule, or at least one add anhydride group per molecule, which add groups are preferably carboxylic add groups -C(0)-0H, or in a polycondensation reaction from compounds Bb having at least one hydroxyl group per molecule and at least one carboxylic add group per molecule.
  • UES self-emulsified
  • the polymer US is preferably a polyester UE which is self-emulsified (UES), with ester groups formed in a transesterification reaction from alkyl esters of malonic add Bm with a hydroxyfunctional component Dh, which is preferably a polyester polyol and/or, more preferably, one or more cydoaliphatic or branched aliphatic diols Bh having from five to fifteen carbon atoms, wherein at least one is most preferably selected from the group consisting of neopentylglycol, 1,2-, 1,3- and 1,4- bishydroxymethylcydohexane, 2-sec-butyl-2-methyl-propanediol-l,3, 2-butyl-2-ethyl- propanediol-1,3, 2-ethyl-propane-diol-l,3, 2-butyl-2-methyl-propanediol-l,3, 2,6- bishydroxymethyldecahydronaphthalene, and the
  • polymer US is a polyurethane UU which is self-emulsified (UUS), having methane groups -C-N(H)-C(0)-0-C- in the polymer chain, which methane groups are formed in a polyaddition reaction from hydroxy-functional polymeric compounds B having at least two hydroxyl groups per molecule, and from isocyanate-functional compounds Di having at least two isocyanate groups per molecule.
  • Useful Michael donor groups are derived from malonic acid, from acetoacetic add, from cyanoacetic add, and from acetamido compounds.
  • At least difunctional constituents are needed for polymerisation, more than two reactive groups per molecule of the binder composition are needed for crosslinking of the coating film. A balance must be found between the needed degree of crosslinking for hardness and chemical and solvent resistance, and avoiding brittleness of the film due to a too high degree of crosslinking.
  • Da and Di in a two-step reaction is also a preferred embodiment, preferably first building a hydroxy-functional polyester using Da to attach hydroxy-functional molecules B, alone or together with one or more of the optional components, to each other, which polyester is then reacted, alone or together with one or more of the optional components, with Di under formation of a polyester-urethane.
  • Da is a reactive derivative of a dibasic add that is able to react with the oligomeric or polymeric hydroxy-functional component B, and optionally, also with compounds A that are hydroxy-functional and are hydrophilic, as used in the synthesis of the self-emulsifying polymers US.
  • add anhydrides would generate add groups
  • other reactive derivatives of adds particularly isopropenyl esters or esters of other enols, which are split off as isopropenol molecules which immediately convert to their tautomeric form, acetone, which can be removed by distillation. In this way, no add groups are generated which would interfere with the basic catalysis of the Michael reaction.
  • the compounds Di are preferably diisocyanates which are well known for formation of polyurethanes.
  • Commonly used diisocyanates are the aliphatic isocyanates having from four to twenty carbon atoms, preferably, 1,4-diisocyanatobutane, 1,6-diisocyanatohexane, cydoaliphatic diiso-cyanates such as isophorone diisocyanate, 1,4-cydohexane diisocyanate, bis-(4-isocyanato-hexyl)methane, and aromatic diisocyanates such as tetramethylxylylenediisocyanate, toluene diisocyanate and bis-(4-isocyanatophenyl)methane.
  • the polymeric hydroxy-functional component B used for the synthesis of polymers US is selected from the group consisting of
  • polyesterpolyol B1 comprising malonate moieties, calculated as -CO-CH2-CO- with a molar mass of 70.05 g/mol, in a mass fraction of at least 7%, more preferably at least 15 %,
  • a polyamide polyol B4 comprising groups derived from acetoacetamide, and mixtures of two or more of Bl, B21, B22, and B4.
  • biobased monomers Generally as an alternative to petrochemical based monomers the use of biobased monomers is also preferable. Isosorbide or other dianhydrohexitoles can preferably be used as hydroxy- functional component for the synthesis of polyester. Dimer fatty adds can preferably be used as a dicarboxylic adds for the synthesis of polyester. Dimer diols made from dimerised fatty adds by hydrogenation can preferably be used for the synthesis of polyester. Instead of petrochemical based dialkylmalonate preferably biobased grades of dialkylmalonate can be used that is prepared through a microbial process using acid-tolerant yeasts, starting from sugar and CO2.
  • the polymers US comprising Michael donor groups are self-emulsifying polymers US comprising urethane groups as repeating units, moieties derived from a hydroxy-functional component A having at least one hydrophilic group, and containing a spedfic amount of substance of addic C-H groups of at least 0.5 mol/kg, derived from malonate moieties.
  • Those preferred polymers preferably also contain ester groups as repeating units.
  • the hydroxy-functional component A is preferably selected from components Anl2, optionally in the presence of one or more component Aa, as described here above.
  • the specific amount of addic C-H groups is more preferably of at least 1.2 mol/kg, most preferably at least 2.0 mol/kg.
  • the addic C-H groups are preferably derived from malonate moieties.
  • hydroxy-functional component B having acidic C-H groups that is a polyester polyol, more preferably a polyester BM, with a hydroxy-functional component A and a isocyanate-functional compound Di as described here above, and optionally with one or more further hydroxy- functional components B" as described here above, in particular with low molar mass dihydroxy compounds B"h and/or polycarbonatediols BC and/or polyesterdiols BE.
  • the polyester polyol used as hydroxy-functional component B having addic C-H groups in this first variant of the invention is preferably a polyester polyol having a glass transition temperature Tg of at least -50 °C, more preferably at least -25 °C, more preferably at least 0°C.
  • the polymers US comprising Michael donor groups and urethane groups as repeating units according to this first variant of the invention preferably has a mass average molar mass of at least 5000, preferably at least 8000 g/mol.
  • the mass average molar mass does preferably not exceed 15000, more preferably not 12000, g/mol.
  • the amount of Anl2 in this polymer US of this first variant is preferably such that the amount of oxyalkylene, espedally oxyethylene, in the overall polymer US is from 5 to 50 weight %, more preferably from 10 to 30 wt% and most preferred from 12 to 20 wt%.
  • the amount of Anl2 in this polymer US is preferably such that the amount of oxyalkylene, espedally oxyethylene, in the overall polymer US is from 5 to 150 g per mol of addic C-H group, more preferably from 10 to 100, and most preferred from 10 to 75 g per mol of addic C-H group.
  • the polymers US comprising Michael donor groups are self-emulsifying polymers US comprising ester groups as repeating units, moieties derived from a hydroxy-functional component A having at least one hydrophilic group, and containing a specific amount of substance of addic C-H groups of at least 0.5 mol/kg, derived from malonate moieties.
  • the hydroxy-functional component A is preferably selected from components Anl2, optionally in the presence of one or more component Aa, as described here above.
  • Those preferred polymers are preferably obtained by reacting an alkyl ester of malonic add Bm, as described here above, with a hydroxy-functional component A and one or more further hydroxy -functional components Dh, and optionally one or more hydroxyfunctional components B" as described here above, in particular with low molar mass dihydroxy compounds B"h.
  • dialkyl malonates Bm espedally those having alkyl groups of from one to four carbon atoms, such as dimethylmalonate, diethylmalonate, di-n-propylmalonate, diisopropyl-malonate, di-n-butylmalonate, and diisobutylmalonate.
  • the specific amount of addic C-H groups in the polymer US is more preferably of at least 2.0 mol/kg, most preferably at least 5.0 mol/kg.
  • the addic C-H groups are preferably derived from malonate moieties.
  • preferred components Dh are polyesterpolyols and/or cydoaliphatic or branched aliphatic diols Bh ; particularly preferred components Dh are cydoaliphatic or branched aliphatic diols Bh having from five to fifteen carbon atoms, wherein at least one is preferably selected from the group consisting of neopentylglycol, 1,2-, 1,3- and 1,4- bishydroxymethylcydohexane, 2-sec-butyl-2-methyl-propanediol-l,3, 2-butyl-2-ethyl- propanediol-1,3, 2-ethyl-propane-diol-l,3, 2-butyl-2-methyl-propanediol-l,3, 2,6- bishydroxymethyldecahydronaphthalene, and the isomer mixture of TCD alcohol (tricydodecanedimethanol or octahydro-4,7-methano-
  • Those preferred polymers can also be obtained by reacting an alkyl ester of malonic acid Bm, as described here above, with a polyester polyol which comprises said hydroxy-functional component A and is obtained by reacting said component A with one or more acid- functional compounds having at least two add groups per molecule, or at least one add anhydride group per molecule, which acid groups are preferably carboxylic acid groups - C(0)-OH , and optionally one or more hydroxyfunctional components B" as described here above, in particular with low molar mass dihydroxy compounds B"h.
  • the add functional compound is preferably an aliphatic or aromatic diacid or anhydride having at least four, and not more than twelve carbon atoms, more preferably selected from the group consisting of sucdnic add, adipic acid, 1,2-, 1,3-, and 1,4-cydohexanedicarboxylic add, terephthalic add, isophthalic acid, hexahydrophthalic acid or anhydrides thereof.
  • the polymers US comprising Michael donor groups and ester groups as repeating units according to this second variant of the invention preferably has a mass average molar mass of at least 1500, preferably at least 2000 g/mol.
  • the mass average molar mass does preferably not exceed 7500, more preferably not 5000, g/mol.
  • the amount of Anl2 in this polymer US of this second variant is preferably such that the amount of oxyalkylene, espedally oxyethylene, in the overall polymer US is from 5 to 50 weight %, more preferably from 10 to 30 wt%.
  • the amount of Anl2 in this polymer US is preferably such that the amount of oxyalkylene, espedally oxyethylene, in the overall polymer US is from 5 to 150 g per mol of addic C-H group, more preferably from 10 to 100, and most preferred from 10 to 75 g per mol of addic C-H group.
  • the self-emulsifying polymer US according to the invention may be dispersed in water.
  • the aqueous polymer dispersion according to the invention is obtained by dispersing one or more self-emulsifying polymer US according to the invention in water, optionally containing one or more other components.
  • the said self-emulsifying polymer US comprising Michael donor groups or aqueous polymer dispersion of polymer US is combined with a second component hereinafter referred to as "Michael acceptor" MA which is at least one organic compound having at least two activated olefinically unsaturated groups of formula
  • the Michael acceptor can be a monomeric, oligomeric or polymeric compound, and it is also possible, within the scope of the present invention, that the same polymer may carry both Michael donor groups and Michael acceptor groups.
  • Michael acceptor groups can be done by adding Michael acceptor groups that are chemically bound to the backbone of the polymer US, usually by using a further constituent E in the synthesis of the polymer US which has at least one, preferably two, hydroxyl groups, and at least one activated olefmically unsaturated group.
  • Michael acceptor groups can also be done by a carrier compound different from the polymer US carrying Michael acceptor groups, preferably to an oligomeric or polymeric carrier compound, which preferably is co-emulsified in the polymer dispersion of polymer US or blended therewith.
  • the addition of Michael acceptor groups can be done by a combination of both, i.e. by adding Michael acceptor groups chemically bound to the backbone of the polymer US and Michael acceptor groups chemically bound to a carrier compound different from the polymer US.
  • Suitable components MA are therefore ethylenically unsaturated components in which the carbon-carbon double bond is activated by an EWG, which is preferably a carbonyl group, a carboxylic add group, a cyano group, or a nitro group.
  • EWG ethylenically unsaturated components in which the carbon-carbon double bond is activated by an EWG, which is preferably a carbonyl group, a carboxylic add group, a cyano group, or a nitro group.
  • EWG ethylenically unsaturated components in which the carbon-carbon double bond is activated by an EWG, which is preferably a carbonyl group, a carboxylic add group, a cyano group, or a nitro group.
  • Representative examples of such components are disdosed in US 2,759,913 A, column 6, line 35, to column 7, line 45, DE 835 809 B, column 3, lines 16 to 41, US 4,871,822 A, column 2, line 14, to column
  • the component MA is an unsaturated acryloyl functional component.
  • a first preferred group of suitable components MA are acrylic esters of hydroxyfunctional compounds having from 2 to 6 hydroxyl groups and from one to twenty carbon atoms. These esters may optionally contain hydroxyl groups. Espedally preferred examples indude hexanediol diacrylate, trimethylol propane triacrylate, pentaerythritol triacrylate, and di-trimethylolpropane tetraacrylate.
  • a further preferred group of compounds are polyesters based on maleic, fumaric and/or itaconic add, and anhydrides thereof if they exist, and on divalent or polyvalent hydroxyl compounds, optionally also induding minor amounts of monovalent hydroxyl and/or carboxyl compounds. Still further preferred group are polyesters, polyurethanes, polyethers and/or alkyd resins containing pendant activated unsaturated groups.
  • urethane acrylates obtained by reaction of a polyisocyanate with an hydroxyl group-containing acrylic ester, e.g., an hydroxyalkyl ester of acrylic add or a component prepared by esterification of a polyhydroxyl component with less than a stoichiometric amount of acrylic acid; polyether acrylates obtained by esterification of an hydroxyl group- containing polyether with acrylic acid; polyfunctional acrylates obtained by reaction of an hydroxyalkyl acrylate with a polycarboxylic add and/or a polyamino resin; polyacrylates obtained by reaction of acrylic add with an epoxy resin; and polyalkylmaleates obtained by reaction of a monoalkylmaleate ester with an epoxy resin and/or an hydroxy functional oligomer or polymer.
  • activated unsaturated group-containing components MA are acryloyl functional compounds. It is also espedally preferred that the add value of the activated unsaturated group-containing components is suffidently low to not substantially impair the activity of the catalyst, preferably less than about 20 mg/g, and most preferably less than 15 mg/g. These and other activated unsaturated group-containing compounds and their methods of production are generally known to those skilled in the art.
  • the functionality i. e. the number of activated olefmically unsaturated groups in one molecule, is from two to twenty.
  • the number average molar mass of the compounds MA is preferably between 200 g/mol and 5000 g/mol.
  • the specific amount of substance of olefmically unsaturated groups in the compounds MA is preferably from 0.5 mol/kg to 12 mol/kg, corresponding to an "equivalent weight" which is the ratio of the number average molar mass and the number of reactive functional groups per molecule, of from 80 g/mol to 2000 g/mol.
  • Useful Michael acceptors are at least difunctional olefmically unsaturated compounds with carbon-carbon double bonds that are activated by electron-withdrawing groups.
  • Esters of olefmically unsaturated carboxylic adds with multifunctional alcohols which are optionally alkoxylated, or oligomeric compounds comprising esters of olefmically unsaturated carboxylic adds are preferred, particularly esters of acrylic acid.
  • the Michael acceptor which has preferably acryloyl functions as functional moieties can be introduced into the polyurethane by adding esters of multivalent alcohols that are not fully esterified with olefmically unsaturated carboxylic acids, particularly acrylic add, to an isocyanate functional polyurethane prepolymer.
  • Michael acceptor examples include hydroxyethyl acrylate, penterythritol triacrylate, and dipentaerythritolpentaacrylate, or acrylic esters from alkoxylated multivalent alcohols, which lead to concentration of the Michael acceptor groups at the chain end(s) if monohydroxy compounds are used.
  • Further Michael acceptor can be introduced to polymer US by adding reaction products of glyddylethers and olefmically unsaturated carboxylic adds.
  • these Michael Acceptor compounds contain more than one hydroxy group and are therefore reacted into polymer US along the main chain.
  • bisphenol a diglyddyl ether diacrylate is used.
  • Another embodiment comprises addition of resinous compounds having Michael acceptor groups, also preferably acryloyl groups.
  • resinous compounds having Michael acceptor groups also preferably acryloyl groups.
  • These include polyurethanes that comprise acryloyl groups, which generally are compatible with the polyurethanes according to this invention which have addic C-H groups.
  • oligomeric compounds having acryloyl functional groups particularly those that are based on reaction products of partially acrylated multivalent alcohols, which may also be alkoxylated before esterification with acrylic add.
  • Michael acceptor groups are chemically bound to a carrier compound different from the polymer US, preferably to an oligomeric or polymeric ether or urethane compound such as a polyhydroxypolyether or a polyhydroxy urethane, which is co-emulsified in the dispersion of polymer US or blended therewith.
  • a carrier compound different from the polymer US preferably to an oligomeric or polymeric ether or urethane compound such as a polyhydroxypolyether or a polyhydroxy urethane, which is co-emulsified in the dispersion of polymer US or blended therewith.
  • both carrier molecules having Michael acceptor groups, and polymers US having Michael acceptor groups chemically bound to their backbone can be combined in a binder dispersion.
  • These systems can be prepared by adding, during the synthesis of polymer US, a mixture of a fully esterified polyhydroxy compound, and a partially esterified polyhydroxy compound, where esterification is effected by an olefinically unsaturated carboxylic add, preferably acrylic add.
  • Such mixtures are also available commerdally, e. g., mixtures of pentaerythritol triacrylate and pentaerythritol tetraacrylate.
  • Particulary suitable Michael acceptor compounds MA in the present invention are water- based energy curable compositions, espedally water-dispersible urethane acrylates.
  • Such components can be prepared from the reaction of (1) at least one polyisocyanate; (2) at least one hydrophilic compound containing at least one reactive group capable to react with isocyanate groups and making the polymer dispersible in water; (3) at least one compound containing at least one reactive group capable to react with isocyanate groups and at least one ethylenically unsaturated group; (4) optionally at least one polyol like (4a) an aliphatic, cycloaliphatic or aromatic polyol, (4b) a polyester polyol, (4c) a polyether polyol, (4d) a polycarbonate polyol (4e) a polyacrylic polyol, (4f) a polyvinyl polyol (4g) a polysiloxane polyol; (5) optionally, at least one chain capper or extender containing at least one primary or secondary amine function capable to react with isocyanate groups.
  • the water-dispersible urethane acrylate polymer is typically obtained by a multiple-step process operating with or without solvent and from moderate to high temperature (35 to 100°C) taking into account the desired polymer architecture and the subsequent reactant stoichiometry (namely isocyanate / hydroxyl and amine ratios); the control of allophanates and biurets formation at higher temperature can be used to increase the molecular weight and the branching of the polymer.
  • the reaction typically proceeds with usual polymerization aids including catalysts and radical inhibitors; typically the compositions are free of tin. In the case a process solvent is used, it can be stripped out of the product after dispersion in water at a moderate temperature (40-60°C) and under vacuum.
  • the water-based dispersion of the urethane acrylate is containing a limited amount of addic protons hindering the action of the latent base catalyst capable to generate the malonate salt and induce thermal crosslinking.
  • Nonionic polymer stabilization is therefore preferred but can be advantageously balanced with a partial anionic polymer stabilization providing that the acidic form is minor over its conjugated base. The level of the anionic stabilization can be reduced in the case that the polymer contains non-ionic water- solubilizing groups.
  • the hydrophilic compounds (2) containing at least one reactive group capable to react with isocyanate groups and making the polymer dispersible in water are preferably constituted from both anionic and nonionic spedes that ensure an optimal pupe size of the polymer dispersion and a good colloidal stability.
  • a full nonionic polymer stabilization is however possible.
  • Neutralizing agents that may be required for converting addic groups built in the polymer into a salt are either volatile organic bases (like triethylamine) or non-volatile inorganic bases (like sodium hydroxide); the latter has the particularity to stay attached to the polymer all over film formation and thereafter.
  • the resulting anionic functionality present in the form of a carboxylate salt, a sulfonate salt or a phosphonate salt, is usually between 0-40 mgKOH/g, preferably between 2-20 mgKOH/g, more preferably between 4-10 mgKOH/g, the most preferably between 6-8 mgKOH/g.
  • the nonionic functionality preferably present in the form of a polyalkyleneoxide segment, is usually between 0-30% expressed as the weight fraction on the total polymer constituents, preferably between 6-18%; more preferably between 8-16%, the most preferably between 10- 14%.
  • the polyalkyleneoxide can be a homopolymer or a copolymer, either random or block, with a molecular weight between 200 - 20,000 Daltons, preferably between 500 - 5,000 Daltons, more preferably between 500 - 2,500 Daltons, most preferably between 500 - 1,500 Daltons; the polyalkyleneoxide is preferably polyethyleneoxide with a molecular weight between 500 - 1,500 Daltons.
  • the polyethyleneoxide is preferably used as a 1,3-diol capable to orient its hydrophilic moiety as a pendant chain of the main polyurethane chain - in opposition to telechelic polyethyleneoxide diols or their equivalent polyester diols, polycarbonate diols or other associated polymers.
  • the weight ratio between the alpha-(2,2-bis(hydroxymethyl)butyl)-omega-methoxy-poly(oxy-l,2-ethanediyl) monomer, known as YMER® N120 (Perstorp), and the dimethylolpropionic acid is usually fixed between 1:0 and 0:1, preferably between 5:1 and 15:1, most preferably between 8:1 and 12:1, the most preferably at 9:1.
  • the nonionic and anionic polymer stabilization can be present on the same polymer or in separate polymers; this construction has the advantage to control and limit the viscosity increase of the final dispersion as a function of pH.
  • the urethane acrylate polymer of the invention is further characterized by a level of (meth)acrylated functionality above 1 meg/g, preferably above 2 meq/g, more preferably above 3 meq/g, most preferably above 4 meq/g, the most preferably above 5 meq/g.
  • the final dispersion composition of the urethane acrylate, in the frame of the invention presents a pH above 7, preferably above 8, most preferably above 9, the most preferably above 10.
  • the viscosity of this final dispersion is usually below 20,000 mPa.s, preferably below 2,000 mPa.s, more preferably below 1,000 mPa.s, most preferably below 500 mPa.s and the most preferably below 200 mPa.s.
  • Michael acceptor structures are built into the polymer US which comprises Michael donor groups.
  • This can be effected by addition of a component E which is a single compound, or a mixture of compounds which are monomeric, dimeric or oligomeric hydroxy-functional compounds which can also be alkoxylated (ethoxylated or propoxylated, or with mixed oxyalkylation), and which are not fully esterified with olefmically unsaturated carboxylic acids, preferably, acrylic add, i. e., they have still hydroxyl groups which are not esterified.
  • a component E which is a single compound, or a mixture of compounds which are monomeric, dimeric or oligomeric hydroxy-functional compounds which can also be alkoxylated (ethoxylated or propoxylated, or with mixed oxyalkylation), and which are not fully esterified with olefmically unsaturated carboxylic acids, preferably, acrylic add, i. e., they have still hydroxyl groups which are not
  • Michael acceptor components E can be introduced to polymer US by adding reaction products of glyddylethers and olefinically unsaturated carboxylic acids. Preferably these Michael Acceptor compounds contain more than one hydroxy group and are therefore reacted into polymer US along the main chain. Most preferably bisphenol a diglycidyl ether diacrylate is used.
  • the invention also relates to a polymer U and an aqueous polymer dispersion of a polymer U comprising Michael donor groups and Michael acceptor groups.
  • This polymer is preferably a self-emulsifying polymer US which comprises in its polymer chain incorporated moieties that have pending hydrophilic groups, and/or hydrophilic groups which form part of the polymer chain, and wherein the Michael donor groups are acidic C-H groups from activated methylene and/or methine groups, wherein the polymer US, comprises, on average, at least two addic C-H groups per molecule, and wherein the specific amount of substance of addic C-H groups in the polymer US is at least 0.5 mol/kg, preferably at least 1, more preferably at least 1.4, most preferably at least 1.8 and most preferably at least 2.5 mol/kg, and wherein the Michael acceptor groups are activated olefmically unsaturated groups, espedally acryloyl groups.
  • the polymer U or US preferably comprises malonate groups.
  • the polymer U or US preferably has all other features described here above in relation with a polymer US not containing Michael acceptor groups.
  • the polymers US comprising Michael donor groups are self-emulsifying polymers US comprising urethane groups as repeating units, moieties derived from a hydroxy-functional component A having at least one hydrophilic group, and containing a spedfic amount of substance of addic C-H groups of at least 0.5 mol/kg, derived from malonate moieties, and Michael acceptor groups, in particular acrylic groups derived from compounds E as described here above.
  • Those preferred polymers preferably also contain ester groups as repeating units.
  • the hydroxy-functional component A is preferably selected from components Anl2, optionally in the presence of one or more component Aa, as described here above.
  • the spedfic amount of addic C-H groups is more preferably of at least 1.2 mol/kg, most preferably at least 2.0 mol/kg.
  • the addic C-H groups are preferably derived from malonate moieties.
  • hydroxy-functional component B having acidic C-H groups that is a polyester polyol, more preferably a polyester BM, with a hydroxy-functional component A, with a hydroxy-functional acrylate compound E and a isocyanate-functional compound Di as described here above, and optionally with one or more further hydroxy-functional components B" as described here above, in particular with low molar mass dihydroxy compounds B"h and/or polycarbonatediols BC. It is also possible to incorporate, at least partially the component A and/or hydroxy-functional acrylate compound E into the hydroxy-functional component B.
  • the polyester polyol used as hydroxy-functional component B having addic C-H groups in this third variant of the invention is preferably a polyester polyol having a glass transition temperature Tg of at least -50 °C, more preferably at least -25 °C, more preferably at least 0°C.
  • the polymers US comprising Michael donor groups, Michael acceptor groups and urethane groups as repeating units according to this third variant of the invention preferably has a mass average molar mass of at least 5000, preferably at least 8000 g/mol.
  • the mass average molar mass does preferably not exceed 15000, more preferably not 12000, g/mol.
  • the relative amount is preferably from 75 to 250 %. In case no radiation curing is involved, the relative amount is more preferably from 10 to 100 %, most preferably from 20 to 90 %.
  • the polymers U comprising Michael donor groups are self-emulsifying polymers US comprising ester groups as repeating units, moieties derived from a hydroxy-functional component A having at least one hydrophilic group, and containing a specific amount of substance of addic C-H groups of at least 0.5 mol/kg, derived from malonate moieties, and Michael acceptor groups derived from compounds E as described here above.
  • the hydroxy-functional component A is preferably selected from components Anl2, optionally in the presence of one or more component Aa, as described here above.
  • Those preferred polymers are preferably obtained by reacting an alkyl ester of malonic add Bm, as described here above, with a hydroxy-functional component A, with a hydroxy- functional compound E and one or more further hydroxy-functional components Dh, and optionally one or more hydroxyfunctional compounds B" as described here above, in particular with low molar mass dihydroxy compounds B"h.
  • Particulary preferred are dialkyl malonates Bm, especially those having alkyl groups of from one to four carbon atoms, such as dimethylmalonate, diethylmalonate, di-n-propylmalonate, diisopropyl-malonate, di-n-butylmalonate, and diisobutylmalonate.
  • the specific amount of addic C-H groups is more preferably of at least 2.0 mol/kg, most preferably at least 5.0 mol/kg.
  • the addic C-H groups are preferably derived from malonate moieties.
  • preferred components Dh are polyesterpolyols and/or cydoaliphatic or branched aliphatic diols Bh ; particularly preferred components Dh are cydoaliphatic or branched aliphatic diols Bh having from five to fifteen carbon atoms, wherein at least one is preferably selected from the group consisting of neopentylglycol, 1,2-, 1,3- and 1,4- bishydroxymethylcydohexane, 2-sec-butyl-2-methyl-propanediol-l,3, 2-butyl-2-ethyl- propanediol-1,3, 2-ethyl-propane-diol-l,3, 2-butyl-2-methyl-propanediol-l,3, 2,6- bishydroxymethyldecahydronaphthalene, and the isomer mixture of TCD alcohol (tricydodecanedimethanol or octahydro-4,7-methano-
  • Those preferred polymers can also be obtained by reacting an alkyl ester of malonic add Bm, as described here above, with a polyester polyol which comprises said hydroxy-functional component A and/or compound E, and is obtained by reacting said component A and/or compound E with one or more acid-functional compounds having at least two add groups per molecule, or at least one add anhydride group per molecule, which add groups are preferably carboxylic add groups -C(0)-OH , and optionally one or more hydroxyfunctional components B" as described here above, in particular with low molar mass dihydroxy compounds B"h.
  • the add functional compound is preferably an aliphatic or aromatic diadd or anhydride having at least four, and not more than twelve carbon atoms, more preferably selected from the group consisting of sucdnic add, adipic add, 1,2-, 1,3-, and 1,4- cydohexanedicarboxylic add, terephthalic add, isophthalic add, hexahydrophthalic add or anhydrides thereof.
  • the polymer US comprising Michael donor groups, Michael acceptor groups and ester groups as repeating units according to this fourth variant of the invention preferably has a mass average molar mass of at least 1500, preferably at least 2000 g/mol.
  • the mass average molar mass does preferably not exceed 7500, more preferably not 5000, g/mol.
  • the relative amount is preferably from 75 to 250 %. In case no radiation curing is involved, the relative amount is more preferably from 10 to 100 %, most preferably from 20 to 90 %.
  • the water-borne coating composition further comprises a catalyst C to facilitate the Michael addition reaction.
  • catalysts are those described in EP 2 374 836 Al, where a substituted carbonate salt Cl
  • X + being a cation, where R is H (forming a hydrogen carbonate), or linear or branched alkyl from one to twenty carbon atoms, or aralkyl from seven to twenty -five carbon atoms, (both forming ester-carbonates), M + is an alkali cation, an earth alkali cation, an organic ammonium cation R' 4 N + , or an organic phosphonium cation R' * 4 P + , where the groups R' and R" are linear or branched or cyclic alkyl groups having from one to ten carbon atoms, such as methyl, ethyl, isopropyl, n-butyl, 2-ethylhexyl, cydohexyl, and stearyl, or aralkyl from seven to twenty-five carbon atoms, such as benzyl and phenethyl, and may be different from each other in one cation
  • 1,3- diketones such as
  • optional components C2' which have one or more addic Q-H groups wherein Q is selected from the group consisting of nitrogen, phosphorus, oxygen, sulfur, and carbon, the z> anion being a Michael addition donor reactable with a Michael acceptor, wherein the pKa(C2') of the Q-H group in component C2' is more than two lower than the pKa(MD) of the first proton of the Michael donor component and being lower than 10.5, and the ratio n( H, C2') / n( C, C2) of the amount of substance of addic Q-H groups in component C2' to the amount of substance of the carbanion in component C2 is between 0.01 and 50.
  • C2' is preferably an organic amine compound having at least one >NH group where the pKa value (negative decadic logarithm of the ionisation constant Ka) for the reaction >N- H ⁇ H> >N + H + is between 4 and 14.
  • pKa value negative decadic logarithm of the ionisation constant Ka
  • these systems are disclosed in WO 2014/166880 Al.
  • the preferred organic nitrogen compounds are sucdnimide, 1,2,4-triazole, and 1,2,3- benzotriazole.
  • n is an integer equal to, or greater than, one, and A n+ is a cationic spedes or a polymer, with the proviso that A n+ is not H + , and optionally, further comprises ammonium carbamate, H 2 R ,
  • Mixtures of carbamate catalysts C3 and carbonate catalysts Cl which are also preferably used have been described in WO 2018/231 927 Al and also in WO 2018/231 920 Al.
  • the present invention also relates to an aqueous polymer dispersion and to an aqueous coating composition comprising at least one polymer US as described here above.
  • the aqueous polymer dispersion according to the invention preferably also contains Michael acceptor groups, wherein :
  • Michael acceptor groups are chemically bound to the backbone of the polymer US by using a further constituent E in the synthesis of the polymer US which has at least one, preferably two, hydroxyl groups, and at least one activated olefinically unsaturated group
  • Michael acceptor groups are chemically bound to a carrier compound different from the polymer US, preferably to an oligomeric or polymeric carrier compound as described here above, which preferably is co-emulsified in the polymer dispersion or blended therewith, or
  • Michael acceptor groups are chemically bound to the backbone of the polymer US and Michael acceptor groups are chemically bound to a carrier compound different from the polymer US.
  • Particulary suitable Michael acceptor carrier compounds are water-based energy curable compositions, especially water-dispersible urethane acrylates, as described here above.
  • the aqueous polymer dispersion according to the invention can be made by preparing a aqueous dispersion of one or more polymer US and blending therewith or co-emulsifying therein one or more Michael acceptor carrier compound or by blending an aqueous dispersion of one or more polymer US with an aqueous dispersion of one or more Michael acceptor carrier compound or by co-emulsifying or blending one or more polymer US with with an aqueous dispersion of one or more Michael acceptor carrier compound.
  • the present invention also relates to an aqueous coating composition
  • an aqueous coating composition comprising at least one polymer US as described here above, and at least one component comprising Michael acceptor groups, said component may be the same as polymer US if such polymer US comprises also Michael acceptor groups as described here above, and/or may be a component different from polymer US, and at least one catalyst as described here above.
  • the Michael donor is a water-dispersible oligomer or polymer, or both the Michael donor and the Michael acceptor are water- dispersible oligomers or polymers, or both Michael donor groups and Michael acceptor groups are present in a water-dispersible oligomer or polymer.
  • the aqueous dispersion of polymer US comprising Michael donor groups is mixed with the appropriate amount of a Michael acceptor component, taking into account if a Michael acceptor compounds has already been incorporated into the polymer US, or has been added thereto before or during dispersion, pigments, dyes, fillers, and additives such as antisettling agents, dispersants, defoamers, wetting agents, light and UV stabilisers, flow modifiers, adhesion promoting agents, coalescence agents, corrosion inhibitors, matting agents, and flame retardants are added, and the catalyst is added.
  • a Michael acceptor component taking into account if a Michael acceptor compounds has already been incorporated into the polymer US, or has been added thereto before or during dispersion, pigments, dyes, fillers, and additives such as antisettling agents, dispersants, defoamers, wetting agents, light and UV stabilisers, flow modifiers, adhesion promoting agents, coalescence agents, corrosion inhibitors, matting agents, and flame retardants are added, and
  • the activated C-H group of the Michael donor when deprotonated, adds to one of the carbon atoms of the activated olefinically unsaturated group of the Michael acceptor.
  • the activated methylene (>CH2) group can, in principle, be equivalent with two activated methine (oCH) groups. This is, however, only the case for those Michael donor / Michael acceptor combinations wherein both hydrogen atoms of the Michael donor component are reactive; for example in case of a system comprising malonate and acryloyl reactive groups, both hydrogen atoms of the methylene group in the malonate entity can react. In a Michael addition reaction with maleates, this is not the case: the second hydrogen atom of the methylene group is no longer reactive once one maleate molecule has been added.
  • Suitable radiation types for the curing of the polymers according to the invention are UV light and electron beam.
  • Typical suitable UV light sources emit light at wavelengths between 200 and 800 nm and emit at least some radiation in the range 200 to 400 nm.
  • the source of the UV light can for instance be a UV light emitting diode (UV-LED).
  • UV-LED typically emit in a spectrum with the strongest wavelength in the range of from 365 to 395 nm.
  • the source of radiation can also be an Excimer lamp such as one from IOT GmbH at 172 nm.
  • UV light Another example of suitable source of UV light is a medium pressure Hg bulb.
  • a photoinitiator In the case of radiation by UV light, a photoinitiator is usually needed to form free radicals that initiate the polymerisation process during the photocuring reaction, while no additional photoinitiator is needed when using electron beams as radiation.
  • the combination of these two curing reactions leads to faster formation of the cured coating film, and to higher hardness and better solvent resistance of the cured coating film.
  • This dual cure technology also allows to reduce the amount of photoinitiator used in curing with UV light alone, and thus helps to reduce problems with yellowing of the coating films due to higher amounts of photoinitiator present in the coating film.
  • the coating composition of the present invention can also be blended with other organic binder resins in order to improve application parameters, i.e. open time, physical drying performance, adhesion, anti-corrosion performance, solids content.
  • Particularly useful as such blending resins are the ones having a very low level of addity which would interfere with the basic catalysis of the Michael reaction.
  • Particularly useful are acrylic dispersion resins with an add value of less than 10 mg/g (based on solid polymer).
  • Further preferable blending resins are alkyd type resins that are emulsified with polymeric surfactants and that show an add value of less than 10 mg/g (based on solid polymer).
  • Emulsions of epoxy resins stabilized with nonionic surfactants are also particularly preferred. Further nonionic stabilized polyurethane dispersions or emulsions of oil-free polyesters can be used as blending resin.
  • aqueous coating compositions according to the invention can be used in several applications, particularly as topcoat in marine, protective and industrial OEM market applications.
  • usual further components such as fillers, light stabilisers, flow and levelling additives, pigments, pigment wetting agents, antisettling agents, coalescence agents, and bioddes can be added to the coating compositions.
  • the coating compositions in accordance with the present invention are suitable for a variety of coatings uses, for example, as paint, impregnating, sealing and bonding compositions.
  • a preferred application is as a primer, topcoat, basecoat, filler or dearcoat; the coating compositions may be applied to a substrate in any convenient manner such as, for example, by
  • the crosslinkable composition of the invention can be applied onto a wide range of substrates, such as metallic substrates induding iron, steel, pretreated steel types such as electrocoated, zinc (galvanized), and phosphated steel, oxilan-pretreated steel, shot/grit-blasted steel, tinplate, aluminium substrates induding chrome treated and non-chrome treated aluminium or alloys.
  • substrates such as metallic substrates induding iron, steel, pretreated steel types such as electrocoated, zinc (galvanized), and phosphated steel, oxilan-pretreated steel, shot/grit-blasted steel, tinplate, aluminium substrates induding chrome treated and non-chrome treated aluminium or alloys.
  • the crosslinkable composition of the invention can also be applied on wooden substrates or wood composites, board, paper, cardboard, leather, synthetic material, glass and mineral substrates such as concrete, tiles, stone and plaster.
  • substrates for the crosslinkable composition of the invention are heat sensitive substrates such as plastic substrates, especially ABS substrates, polycarbonate substrates, AB S/polycarbonate substrates, glass- and carbon-fiber reinforced plastics or composites, SMC (sheet molding compound) such a polyester and glass fiber combinations, especially those used in automotive applications, polyethylene terephthalate), poly(butylene terephthalate), polyamide-6, polyamide-6.6, (thermoplastic) polyolefins, poly(vinyl chloride), poly(methyl methacrylate) and polystyrene.
  • plastic substrates especially ABS substrates, polycarbonate substrates, AB S/polycarbonate substrates, glass- and carbon-fiber reinforced plastics or composites
  • SMC sheet molding compound
  • polyester and glass fiber combinations especially those used in automotive applications
  • polyethylene terephthalate poly(butylene terephthalate)
  • polyamide-6 poly(butylene terephthalate)
  • polyamide-6 polyamide-6
  • polyamide-6.6 thermo
  • the crosslinkable composition of the invention can also be applied on coated substrates, including metal, plastic, mineral or wood substrates pretreated with e.g. sealer, primer, putty, water-borne or solvent-borne basecoat layers.
  • suitable primer systems include two-component systems such as two-component solvent-borne or water-borne polyurethanes, aspartate, epoxy-amine, acetoacetate-ketimine and Real Michael Addition compositions or combinations / hybrids thereof, unsaturated polyester putties, one- component coatings such as (thermoplastic) polyacrylics, solvent- or water-borne polyurethanes, urethane acrylic polymers, carboxyl functionalized self-crosslinking acrylic polymer, cationic acrylic polymers or polyvinyl acetate.
  • the crosslinkable composition of the invention can furthermore be applied onto metal, wood or mineral substrates pretreated with adhesion-promoting substances such as (amino)silanes.
  • the coating system may also be applied on multisubstrate assemblies composed of metal and/or plastic parts with various different pretreatments and/or coatings including those mentioned above.. Curing of the above-described coating compositions is preferably carried out at temperatures above about 0 C, generally between about 5 °C and about 150 °C, preferably at from 5 °C to 60 °C, and most preferably between 5 °C and 30 °C (also comprising room temperature).
  • the present invention further relates to a coated substrate which has been coated with a coating composition comprising the aqueous dispersions comprising a polymer US or the coating compositions comprising the polymer US as described here above and wherein the coating composition has cured at a temperature above 0 °C and optionally, additionally, by exposure to radiation, and wherein the coating composition preferably contains a photoinitiator if UV light is chosen as source of radiation.
  • combinations of catalysts C with dispersions of the polymer US comprising Michael donor groups, and further compounds comprising Michael acceptor groups, or combinations of catalysts C with dispersions of polymers US which further comprise Michael acceptor groups in this polymer can also be used as binder system in polymer concrete, together with the usual further concrete constituents which are commonly referred to as "construction aggregate” or simply “aggregate”, and comprise coarse to medium sized particulate material including sand, gravel, crushed stone and crushed slag, and also recycled comminuted concrete, and extenders and fillers, such as fly ash, and rock flour.
  • Another preferred application is as a binder system for In-Mold Decoration (IMD) processes as described in EP2408605, WO9304837, US2019375139 or US2019381821 in which decorative films are placed into an injection mold and back-injected with a polymer melt.
  • IMD In-Mold Decoration
  • Particularly suitable is the application as a clearcoat for the process described in US2019381821 in which the decorative film is applied as a transfer film that must easily be removable from the clearcoat after molding.
  • the polymer composition of the invention can further be used as a binder for inks, print receptive coatings and overprint varnishes.
  • digital printing inkjet
  • 3D printing can be used.
  • malonate-based polymers show a lower propensity for discolouration in contact with metal ions as compared to acetoacetoxy based polymers, such as used in US 5,567,761 A
  • the specific amount of substance « m (F) of a certain functional group F in a chemical compound B is calculated as the amount of substance «( F) of the said functional group, divided by the mass m( B) of the compound B under consideration (the mass of the solid or undiluted compound B in the case that a solution or dispersion of the said compound B is used).
  • the appropriate SI unit is "mol/kg”; formerly, the reciprocal value of this quantity was also used, with the deprecated designation as "equivalent weight” with the unit "g/mol",
  • the "amine value”, also referred to as "amine number” is the ratio WAm of the mass « ⁇ ko H of potassium hydroxide that needs the same amount of substance of an add for neutralisation as a mass m B of an amine-functional organic substance B which has an amount of substance «Am of basic amino groups Am, and the said mass mv.
  • the dynamic viscosity h was determined in a cone-plate viscometer at 25 C and a shear rate of 100 s 1 if not stated otherwise,
  • a sample was dissolved in (60 ⁇ 1) mL of dimethylformamide (DMF, dry, pro analysi grade) in an Erlenmeyer flask of 100 mL capacity, three drops of a solution of azo violet solution (4-(4-nitrophenylazo)-resorcinol, dissolved in o- xylene, mass fraction of solute 0.5 %) was added, and the flask was immediately stoppered with a flexible sleeve stopper with an N2 inlet tube and flushed with nitrogen during the whole measurement process to avoid CO 2 consumption, titration was done manually with a sodium methoxide solution (Na OCH3 dissolved in methanol, pro analysi grade, mass fraction of solute 25 %) from a syringe until a clear blue colour appears at the equivalence point.
  • DMF dimethylformamide
  • the amount of titrant solution was determined gravimetrically by weighing the complete syringe before and after addition.
  • the titre of the sodium methoxide solution was determined indirectly by adding a specified amount to water, and by titration of the sodium hydroxide formed with an HC1 solution with potentiometric indication.
  • Diethylmalonate (DEM) has been applied as a reference. and the following abbreviations have been used:
  • di-TMPA3 di-trimethylolpropane triacrylate having a hydroxyl value of 136 mg/g, and a specific amount of substance of olefinically unsaturated groups of 7.30 mol/kg (corresponding to a "double bond equivalent weight" of 137 g/mol)
  • EOPO-PEA4 ethoxylated/propoxylated pentaerythritol tetraacrylate, wherein the ratio of oxyethylene units to oxypropylene units to pentaerythritol units is 4 mol : 1 mol : 1 mol, having a specific amount of substance of olefinically unsaturated groups of 6.82 mol/kg, corresponding to a "double bond equivalent weight" of 146.7 g/mol
  • EO-TMPTA tri-ethoxylated trimethylolpropane triacrylate having a specific amount of substance of olefinically unsaturated groups of 7.00 mol/kg, corresponding to a "double bond equivalent weight" of 142.8 g/mol
  • IPDI isophoronediisocyanate, 5-iso-cy ana to-l-[isocyana tomethyl]-l,3,3-tri methyl- cyclohexane
  • PETIA mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate having a specific amount of substance of olefinically unsaturated groups of 10.1 mol/kg, and a hydroxyl number of 120 mg/g
  • Example la 150 g of the polyester polyol horn Example la were mixed with 42 g of Ymer® N120 and heated to 60 °C. Then, 57 g TMXDI, and 24 g of IPDI were added to this mixture and the temperature was kept below 65 °C for one hour. 30 g of dipropyleneglycol-dimethylether were then added. The temperature of the reaction mixture was further increased to 80 °C and maintained until a mass fraction of isocyanate groups in the reaction mixture of 5.5 % was reached. In a second vessel, 300 g of deionised water and 34.1 g of diethanolamine were heated to 30 °C and the urethane prepolymer was added while stirring at 200 min 1 .
  • a polyurethane dispersion was obtained which was cooled down to room temperature (23 °C).
  • the resin dispersion had a mass fraction of solids of 48.8 %, a dynamic viscosity of 1540 mPa-s and an average particle size of 164 nm with a dispersity of 0.31.
  • the resin had a specific amount of substance of CH-addic hydrogen atoms of 3.115 mol/kg, based on the mass of solids ("equivalent weight of addic hydrogen" of 321g/mol).
  • Example lb 76 g of the polyester polyol horn Example lb were mixed with 42 g of Ymer® N120 and heated to 60 °C. Then, 57 g of TMXDI and 24 g of IPDI were added to this mixture and the temperature was kept below 65 °C for one hour. The temperature was then further increased to 135 °C and maintained until a urethane prepolymer with a mass fraction of isocyanate groups in the reaction mixture of 7.4 % was obtained. In a second vessel, 200 g of deionised water and 33.2 g of diethanolamine were heated to 70 °C and the urethane prepolymer was added while stirring at 200 min 1 .
  • the polyurethane dispersion obtained was cooled down to room temperature (23 °C).
  • the resin dispersion had a mass fraction of solids of 38.4 %, a dynamic viscosity of 4445 mPa-s and an average particle size of 71 nm with a dispersity of 0.17.
  • the resin had a specific amount of substance of CH-addic hydrogen atoms of 3.33 mol/kg, based on the mass of solids (corresponding to an "equivalent weight of addic hydrogen" of 300 g/mol).
  • a mixture of 1500 g of Ymer® N120, 3388 g of the malonate polyester polyol of Example la, 935 g of PETIA, 1760 g of EO-TMPTA, 1.8 g of DBTL, and 7 g of hydroquinone monomethyl- ether was heated to 60 C while purging with air. Over the course of two hours, 1293 g of IPDI were added, and the temperature was maintained at 70 C until a mass fraction of isocyanate groups in the reaction mixture of 0.5 % was reached. 468 g of methoxypropanol were then added, and the temperature was maintained until no more isocyanate could be determined.
  • This prepolymer was dispersed in 8400 g of deionised water at a temperature of 50 C. Viscosity was adjusted by addition of further deionised water, and the resin was cooled down to room temperature (23 C).
  • the resin dispersion obtained had a mass fraction of solids of 50.2 %, a dynamic viscosity of 2445 mPa-s and an average particle size of 64 nm with a dispersity of 0.06.
  • a mixture of 1450 g of Ymer® N120, 2050 g of the malonate polyester polyol of Example lb, 1100 g of PC-diol, 2244 g of DPHA, 1.8 g of DBTL, and 7 g of hydroquinone monomethylether was heated to 60 C while purging with air. Over the course of two hours, 1293 g of IPDI were added and the temperature was maintained at 70 C until a mass fraction of isocyanate groups in the reaction mixture of 0.5 % was reached. 906 g of dipropyleneglycol diethylether and 533 g of methoxypropanol were added, and the temperature was maintained until no more isocyanate could be determined.
  • This prepolymer was dispersed in 6700 g of deionised water at a temperature of 50 °C. Viscosity was adjusted by adding further deionised water and the resin dispersion was cooled down to room temperature (23 C).
  • the resin dispersion had a mass fraction of solids of 41.2 %, a dynamic viscosity of 2590 mPa-s and an average particle size of 130 nm with a dispersity of 0.13.
  • a mixture of 1500 g of Ymer® N120, 2050 g of the malonate polyester polyol of Example lb, 1050 g of PC-diol, 935 g of PETIA, 1420 g of di-TMPA4, 1.8 g of DBTL, and 7 g of hydro- quinone monomethylether was heated to 60 C while purging with air. Over the course of two hours, 1293 g of IPDI were added, and the temperature was maintained at 70 C until a mass fraction of isocyanate groups in the reaction mixture of 0.5 % was reached. 435 g of methoxypropanol were added, and the temperature was maintained until no more isocyanate could be determined.
  • This prepolymer was dispersed in 7800 g of deionised water at a temperature of 5011. Viscosity was adjusted by addition of further deionised water, and the resulting resin dispersion was cooled down to room temperature (23 C).
  • the final resin had a mass fraction of solids of 51.0 %, a dynamic viscosity of 2180 mPa-s, and an average particle size of 93 nm with a dispersity of 0.14.
  • a mixture of 1245 g of Ymer® N120, 3388 g of the malonate polyester polyol of Example la, 255 g of PC-diol, 935 g of PETIA, 1760 g of EO-TMPTA, 1.8 g of DBTL, and 7 g of hydro- quinone monomethylether was heated to 60 C while pinging with air. Over the course of two horns, 1293 g of IPDI were added, and the temperature was maintained at 70 C until a mass fraction of isocyanate groups in the reaction mixture of 0.5 % was reached. 468 g of methoxypropanol were added, and the temperature was maintained until no more isocyanate could be determined.
  • This prepolymer was dispersed in 8400 g of deionised water at a temperature of 5011. Viscosity was adjusted by addition of further deionised water, and the resin dispersion was cooled down to room temperature (23 C).
  • the resin dispersion had a mass fraction of solids of 49.9 %, a dynamic viscosity of 1699 mPa-s, and an average particle size of 84 nm with a dispersity of 0.11.
  • a mixture of 1245 g of Ymer® N120, 3388 g of the malonate polyester polyol of Example la, 255 g of PC-diol, 935 g of PETIA, 977 g of EO-TMPTA, 1.8 g of DBTL, and 7 g of hydroquinone monomethylether was heated to 60 C while purging with air. Over the course of two hours, 1293 g of IPDI were added, and the temperature was maintained at 70 °C until a mass fraction of isocyanate groups in the reaction mixture of 0.5 % was reached. 468 g of methoxypropanol were added and temperature maintained until no more isocyanate could be determined.
  • this prepolymer was dispersed in 6200 g of deionised water at a temperature of 50 C. Viscosity was adjusted with further deionised water and the resin was cooled down to room temperature (25 C).
  • the resin thus obtained had a mass fraction of solids of 45.7 %, a dynamic viscosity of 1280 mPa-s, and an average particle size of 82 nm with a dispersity of 0.10.
  • this prepolymer was dispersed in a mixture of 6300 g of deionised water and 95 g of diethanolamine at a temperature of 30 C. Viscosity was adjusted by addition of further deionised water and the resin was cooled down to room temperature (25 C). The resin obtained had a mass fraction of solids of 44.7 %, a dynamic viscosity of 1980 mPa-s, and an average particle size of 92 nm with a dispersity of 0.15.
  • Example 11 Blend of Polyurethane Dispersion with Malonate Functionality and Acryloyl- Functional Polyurethane Dispersion
  • the mixture was stirred for two horns and was used for formulation after one week of storage at room temperature (2311).
  • the coated panels were stored at 23 H/50 % relative humidity before further testing.
  • Example 14 Application test - Polyurethane Dispersion with Malonate and Acryloyl Functionality and Different Michael Addition Catalysts
  • Example 16 Application test - Polyurethane Dispersion with Malonate and Acryloyl Functionality and Different Michael Addition Catalysts
  • Example 15 White Topcoat Based on Polyurethane Dispersion with Malonate and Acryloyl Functionality
  • a grinding formulation was mixed according to the following redpe of table 5, and ground in a bead mill:
  • This grinding formulation was let down with further 149 g of the resin from Example 9.
  • the catalyst package (0.32 g of an aqueous sodium hydroxide solution having a mass fraction of dissolved NaOH of 10 %, 5.5 g of an aqueous solution of tetrabutylammonium bicarbonate solution having a mass fraction of dissolved salt of 50 %) was added.
  • This coating was applied onto glass plates and steel panels coated with a cured water-based 2-pack epoxy primer in a wet film thickness of 200 pm, the first set a samples one hour after mixing in the catalyst, and the second set of samples seventy -two hours after mixing in the catalyst. After thirty minutes of flash-off, the clearcoats were either cured at room temperature (23 G) and 50 % of relative humidity ("RT cure”), or forced cured for
  • the resin dispersion had a mass fraction of solids of 48.8 %, a dynamic viscosity of 1540 mPa-s and an average particle size of 164 nm with a dispersity of 0.31.
  • the resin had a specific amount of substance of CH-addic hydrogen atoms of 3.115 mol/kg, based on the mass of solids ("equivalent weight of addic hydrogen" of 321g/mol).
  • Viscosity was adjusted by addition of further 16.5 g of water to a dynamic viscosity of 1870 mPa-s, the mass fraction of solids was then 52.7 %.
  • Example 21 Synthesis of a Malonate Polyester with Co-Emulsified Michael Acceptor
  • This mixture was dispersed into 255 g of deionised water; viscosity was adjusted by addition of further 28 g of deionised water to obtain a dynamic viscosity of 2167 mPa-s and a mass fraction of solids of 52.1%.
  • this prepolymer was dispersed in a mixture of 6300 g of deionised water, 81 g of diethanolamine, and 120 g of an aqueous sodium hydroxide solution with a mass fraction of solids of 50 %, at a temperature of 30 C. Viscosity was adjusted by addition of further deionised water and the resin cooled down to room temperature. The final resin had a mass fraction of solids of 34.8%, a dynamic viscosity of 700 mPa-s, and an average particle size of 60 nm with a dispersity of 0.37.
  • Example 24 Formulation of Clearcoat Coating Compositions For Combined Radiation and Thermal Curing
  • the components listed in table 8 were mixed in the given sequence in a lab blender. If necessary the viscosity of the coating composition was further reduced by the addition of deionised water.
  • the dearcoat coating compositions were applied onto substrates (glass plates for pendulum hardness determination) with a lab applicator in a wet film thickness of 200 pm.
  • the coating compositions were either cured by UV radiation (800 mj/cm 2 , Fig lamp) and/or thermally at 23 C and 50 % relative humidity only, or forced cured for thirty minutes at 8011, or for fifteen hours at 7011.
  • the sample that was thermally cured for thirty minutes at 80 U was as well UV cured after thermal crosslinking, to investigate the feasibility of this process.
  • the coated panels were stored at 23 U and 50 % relative humidity for 24 h before further testing.
  • 1 UCECOAT 7738 is a mixed anionically and nonionically stabilized waterbased urethane acrylate with a mass fraction of solids of 38 %, an add value of 0.9 mg/g (based on the mass of the resin dispersion) and a specific amount of substance of
  • 3 OMNIRAD 1173 is a photoinitiator made from 2-hydroxy-2-methyl-l- phenylpropanone (IGM Resins B.V., Waalwijk)
  • IGM Resins B.V., Waalwijk 2-hydroxy-2-methyl-l- phenylpropanone
  • Example 25 Formulation of Yellow Topcoat Compositions For Combined Radiation and Thermal Curing
  • the components listed in the table 9 were mixed in the given sequence in a lab blender.
  • the pigmented coating compositions were applied with a lab applicator onto the substrates (glass plates for Persoz hardness and sanded kitchen board for scratch and acetone resistance) as a wet film thickness of 120 pm followed by 30 min drying at room temperature (23 C) and 15 minutes flash-off at 60 C only when indicated).
  • the coatings were cured by UV radiation (5 m/min @ 80 W/cm, Ga + Hg lamp).
  • the coated panels were stored at 23 G and 50 % relative humidity for 24h before further testing of hardness, mar and chemical resistance.
  • the hardness was measured using Persoz pendulum equipment according to standard ASTM D4366-16, test method B.
  • LUCONYL® NG Yellow 1995 is a proprietary oxide yellow pigment paste composition from BASF consisting of finely grinded pigments dispersed and stabilized in water at a solid content of 60%.
  • AMP-95 is a neutralizer from Angus Chemicals containing 2-amino-2-methyl-l -propanol with 5% added water.
  • OMNIRAD® 2010 is a photoinitiator from IGM Resins made from 2-hydroxy-2-methyl-l- phenyl-propan-l-one and phenylbis(24,6-trimethylbenzoyl)phosphine oxide.
  • BYK® 093 is a proprietary silicone-containing defoamer from Byk.
  • BYK® 378 is a proprietary wetting agent from Byk containing a polyether-modified dimethylpolysiloxane.
  • TEGO® Glide 432 is a proprietary flow additive and wetting agent from Evonik made from a polyether siloxane copolymer.
  • EXILVA® F01-L is a proprietary rheology modifier from Borregaard made from multifunctional micro-fibrillated cellulose.
  • binder composition particularly interesting for dual-cure applications where it brings a strong performance and robustness in the presence of high-opacity pigments (other than white) preventing an easy UV light penetration and a deep cure of the coating. It is also particularly valuable for the efficient curing of poorly exposed areas of a complex tridimensional object (shadow curing) or in the case of low energy UV-light (LED lamp, exdmer lamp).
  • Example 26 Polyurethane dispersion with malonate and acryloyl functionality
  • this prepolymer was dispersed in a mixture of 6300 g deionized water and 90 g diethanolamine at a temperature of 30 °C. Viscosity was adjusted with further deionized water and the resin cooled down to room temperature.
  • the final resin had a non volatile content of 48.4 %, a dynamic viscosity of 2700 mPas and a particle size distribution of 57 nm (0.10 PDI).
  • Example 27 Polyurethane dispersion with malonate and acryloyl functionality
  • this prepolymer was dispersed in a mixture of 6300 g deionized water and 86 g diethanolamine at a temperature of 30 °C. Viscosity was adjusted with further deionized water and the resin cooled down to room temperature. The final resin had a non volatile content of 46.5 %, a dynamic viscosity of 2730 mPas and a particle size distribution of 60 nm (0.10 PDI).
  • Example 28 Polyurethane dispersion with malonate and acryloyl functionality
  • this prepolymer was dispersed in a mixture of 6300 g deionized water and 114 g diethanolamine at a temperature of 30 °C. Viscosity was adjusted with further deionized water and the resin cooled down to room temperature. The final resin had a non volatile content of 43.7 %, a dynamic viscosity of 2265 mPas and a particle size distribution of 112 nm (0.13 PDI).
  • Example 29 Polyurethane dispersion with malonate and acryloyl functionality
  • Polycarbonatediol 467.5 g PETIA, 408 g di-TMPA3, 500 g EOPO-PEA4, 595 g di-TMPA4, 1.8 g DBTL and 8.1 g butylhydroxytoluene were heated to 60 °C while purging with air. Over the course of two hours 1293 g IPDI was added and the temperature maintained at 70 °C until an NCO value of 0.7 % was reached. 430 g methoxypropanol were added and temperature maintained for further one hour. Then this prepolymer was dispersed in a mixture of 6300 g deionized water and 104 g diethanolamine at a temperature of 30 °C.
  • Viscosity was adjusted with further deionized water and the resin cooled down to room temperature.
  • the final resin had a non volatile content of 44.8 %, a dynamic viscosity of 2523 mPas and a particle size distribution of 114 nm (0.10 PDI).
  • Example 30 Polyurethane dispersion with malonate and acryloyl functionality
  • Polycarbonatediol 467.5 g PETIA, 408 g di-TMPA3, 500 g EOPO-PEA4, 595 g di-TMPA4, 1.8 g DBTL and 8.1 g butylhydroxytoluene were heated to 60 °C while purging with air. Over the course of two hours 1293 g IPDI was added and the temperature maintained at 70 °C until an NCO value of 0.7 % was reached. 430 g methoxypropanol were added and temperature maintained for further one hour. Then this prepolymer was dispersed in a mixture of 8550 g deionized water and 104 g diethanolamine at a temperature of 30 °C.
  • Viscosity was adjusted with further deionized water and the resin cooled down to room temperature.
  • the final resin had a non-volatile content of 40.0 %, a dynamic viscosity of 2567 mPas and a particle size distribution of 122 nm (0.16 PDI).
  • Example 31 Polyurethane dispersion with malonate and acryloyl functionality
  • this prepolymer was dispersed in a mixture of 8550 g deionized water and 54 g diethanolamine at a temperature of 30 °C. Viscosity was adjusted with further deionized water and the resin cooled down to room temperature. The final resin had a non volatile content of 40.8 %, a dynamic viscosity of 1255 mPas and a particle size distribution of 97 nm (0.28 PDI).
  • Example 32 Polyurethane dispersion with malonate and acryloyl functionality
  • this prepolymer was dispersed in a mixture of 6300 g deionized water and 85 g diethanolamine at a temperature of 30 °C. Viscosity was adjusted with further deionized water and the resin cooled down to room temperature.
  • the final resin had a non-volatile content of 34.8 %, a dynamic viscosity of 1480 mPas and a particle size distribution of 109 nm (0.14 PDI).
  • Example 33 Polyurethane dispersion with malonate and acryloyl functionality 1245 g Ymer N120, 3388 g of Malonate Polyester Polyol of Example la, 255 g Polycarbonatediol, 467.5 g PETIA, 408 g di-TMPA3, 1020 g EOPO-PEA4, 812 g di-TMPA3, 1.8 g DBTL and 8.1 g butylhydroxytoluene were heated to 60 °C while purging with air. Over the course of two hours 1293 g IPDI was added and the temperature maintained at 70 °C until an NCO value of 0.7 % was reached. 430 g methoxypropanol were added and temperature maintained for further one hour.
  • this prepolymer was dispersed in a mixture of 6300 g deionized water and 115 g diethanolamine at a temperature of 30 °C. Viscosity was adjusted with further deionized water and the resin cooled down to room temperature. The final resin had a non-volatile content of 47.4 %, a dynamic viscosity of 2892 mPas and a particle size distribution of 95 nm (0.10 PDI).
  • Example 36 Clearcoat for foil and plastic coatings for In-mould-decoration processes
  • Part 1 100 g of polyurethane dispersion from Example 10 have been mixed with 5 g of methoxypropoxypropanole, 5 g of deionized water and 1 g of a levelling and substrate wetting agent based on polyether modified polysiloxan (ADDITOL® VXW 6503N, allnex).
  • Part 2 Prior to application, 4.8 g of catalyst of Example 15 have been added.
  • Recipe 2 metallic lpack basecoat 268 g of a polyurethane dispersion was mixed with a slurry of 50 g metallic pigment 58 g butylglycol, combined with 100 g of a 3% deionized water solution of a silicate based thickener (LAPONITE®, Byk) and 110 g of a 10% deionized water solution of an acrylic based thickener (RHEOVIS®, BASF).
  • a silicate based thickener LAPONITE®, Byk
  • RHEOVIS® acrylic based thickener
  • the clearcoat (redpe 1) was applied 100 pm wet with a film applicator and cured for 5 minutes at 150 °C on a PET foil without pre-treatment.
  • the metallic basecoat (recipe 2) was applied by spray application with a resulting dry film thickness of 15 pm and again cured for 5 minutes at 150 °C.
  • the whole part was post-cured for 12 hours at 70 °C. After the post-cure a release test was done and the clearcoat plus metallic basecoat could be released from the PET substrate without high force or resulting cracks in the clearcoat layer resulting in a perfect optical appearance and gloss (89 GU at 60 ° angle).
  • this polyester was dispersed into 152 g water and then the dynamic viscosity and solids content adjusted with further water to a viscosity of 2355 mPas and a solids content of 45.1 %.
  • the H-equivalent weight of this polyester was 405 g/mol based on solid resin.
  • Example 40 Malonate Polyesters cured with UV-PUD
  • a white topcoat was formulated according to following redpe on a bead mill. Then the mill base was let down with further resin, butylglycoleacetate and substrate wetting agent.
  • Example 41 Steel panels were coated with water based 2k epoxy primer and cured for 24 hours at 60°C.
  • the topcoat formulation from Example 41 was mixed with the components of following table and applied in a wet film thickness of 150 pm by draw down.
  • the topcoats were cured at 20 °C/50% relative humidity for 7 days.
  • Example 42 Water dispersable Polyurethane with Malonate and Acryloyl Functionality 1245 g of Ymer® N120, 3388 g of the malonate polyester polyol of Example la, 255 g of PC- diol, 467.5 g of PETIA, 408 g of di-TMPA3, 500 g of EOPO-PEA4, 595 g of di-TMPA4, 1.8 g of DBTL, and 8.1 g of butylhydroxytoluene were heated to 60 G while purging with air. Over the course of two hours, 1293 g of IPDI were added and the temperature was maintained at 70 G until a mass fraction of isocyanate groups in the reaction mixture of 0.7 % was reached.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne un polymère auto-émulsifiant US qui comprend des groupes donneurs de Michael, les groupes donneurs de Michael étant des groupes C-H acides provenant de groupes méthylène et/ou méthine activés, une dispersion aqueuse de polymère contenant un mélange de ce dernier avec des composés ayant des groupes accepteurs de Michael qui sont activés par des groupes à insaturation oléfinique, activés par un groupe attracteur d'électrons, et un catalyseur permettant de favoriser la réaction de Michael, un liant de peinture préparé à partir du mélange et du catalyseur, et des compositions de revêtement comprenant le liant de peinture et des additifs appropriés.
PCT/EP2020/052343 2019-02-01 2020-01-30 Liant pour une composition de revêtement aqueuse WO2020157228A1 (fr)

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AU2020215259A AU2020215259A1 (en) 2019-02-01 2020-01-30 Binder for an aqueous coating composition
EP20701655.1A EP3918017A1 (fr) 2019-02-01 2020-01-30 Liant pour une composition de revêtement aqueuse
KR1020217026809A KR20210122265A (ko) 2019-02-01 2020-01-30 수성 코팅 조성물에 대한 결합제
CN202080011529.7A CN113366069B (zh) 2019-02-01 2020-01-30 用于水性涂料组合物的粘结剂
JP2021544531A JP7486501B2 (ja) 2019-02-01 2020-01-30 水性コーティング組成物のためのバインダー
US17/423,002 US20220098406A1 (en) 2019-02-01 2020-01-30 Binder for an aqueous coating composition
CA3125005A CA3125005A1 (fr) 2019-02-01 2020-01-30 Liant pour une composition de revetement aqueuse

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EP19155169.6 2019-02-01
EP19155169.6A EP3689986A1 (fr) 2019-02-01 2019-02-01 Liant pour compositions de revêtement aqueux
EP19163580.4A EP3712190A1 (fr) 2019-03-18 2019-03-18 Liant pour compositions de revêtement aqueux
EP19163580.4 2019-03-18

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CN115626804B (zh) * 2022-11-18 2023-06-02 吉林省圣鑫建筑材料有限公司 一种高强度环氧树脂混凝土材料及其制备方法
KR102586797B1 (ko) 2023-06-28 2023-10-10 주식회사 나인씨엔에프 인공지능 모델 기반 폐배터리 재생을 위한 원료의 유통 처리 시스템 및 방법
KR102650597B1 (ko) 2023-11-07 2024-03-22 주식회사 순수스토리 농수산물 및 가공식품의 온라인 유통 판매를 위한 주문 처리 및 재고 관리 방법, 장치 및 시스템

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CA3125005A1 (fr) 2020-08-06
US20220098406A1 (en) 2022-03-31
KR20210122265A (ko) 2021-10-08
JP7486501B2 (ja) 2024-05-17
CN113366069B (zh) 2023-04-21
AU2020215259A1 (en) 2021-08-05
JP2022519533A (ja) 2022-03-24
CN113366069A (zh) 2021-09-07

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